JPH10305666A - Thermal transfer recording coloring matter, thermal transfer recording sheet, and thermal transfer ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a transfer recorded matter having high concentration of a component for a block transfer sheet by using specific nitrothiazole azo coloring matter as a coloring matter for coloring matter transfer type thermal transfer recording. SOLUTION: Nitrothiazole azo dye represented by a formula I is used for coloring matter transfer type thermal transfer recording, where X indicates hydrogen atom, alkyl group which may be substituted to fluorine atom, alkoxy group, substituted or non-substituted phenoxy group, halogen atom, formylamino group, alkylcarbonylamino which may be substituted to fluorine atom, substituted or non-substituted phenylcarbonylamino group, alkoxycarbonylamino group or substituted or non-substituted phenoxycarbonylamino group, Y indicates hydrogen atom, alkyl group, alkoxy group or halogen atom, R<1> and R<2> independently indicate hydrogen atom, substituted or non-substituted alkyl group, cycloalkyl group, allyl group or substituted or non-substituted phenyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a nitrothiazole azo dye used for dye transfer type thermal transfer recording, a thermal transfer recording sheet and a thermal transfer ink using the same.

[0002]

2. Description of the Related Art Conventionally, color recording technology has been demanded in printers, copiers, facsimile machines, etc.
A color recording technique using ink jet, thermal transfer, or the like is being studied. The thermal recording method is advantageous over other methods because the maintenance and operation of the apparatus are easy and the apparatus and consumables are inexpensive.

[0003] The thermal transfer method is a heat transfer method in which a transfer sheet having a heat-meltable ink layer formed on a base film is heated by a thermal head to melt the ink and transfer-record on a recording medium. And a transfer sheet having an ink layer containing a heat-migrating dye formed on a base film, heated by a thermal head to sublimate and / or thermally diffuse the dye, and transfer-record on a recording medium. Although the dye transfer method is available, the dye transfer method can control the transfer amount of the dye by changing the energy applied to the thermal head, so that gradation recording becomes easy and is particularly advantageous for full color recording.

When a dye is applied to this method, the dye must satisfy the following conditions. Easily sublimate or thermally diffuse under the operating conditions of the thermal recording head. Do not thermally decompose under the operating conditions of the thermal recording head. Having a favorable hue in color reproduction. Large molecular extinction coefficient. Stable against heat, light, moisture, chemicals, etc. Easy synthesis. Excellent ink suitability. There should be no safety issues. Nitrothiazole azo dyes are known as dyes that are advantageously used in the present recording method (JP-A-60-239).
291; JP-A-62-55194; JP-A-62-33688; and JP-A-8-276670.

[0005]

DISCLOSURE OF THE INVENTION The present invention relates to a nitrothiazole azo dye which has better properties than conventionally known nitrothiazole azo dyes and uses the same as a dye transfer type thermal transfer recording dye. It is an object of the present invention to provide a transfer sheet and an ink for a transfer sheet. When the dye of the present invention is used as a component for a black transfer sheet, a high-density transfer recorded matter is obtained.

[0006]

The present invention provides a compound represented by the following general formula (I):

[0007]

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Wherein X is a hydrogen atom, an alkyl group which may be substituted by a fluorine atom, an alkoxy group, a substituted or unsubstituted phenoxy group, a halogen atom, a formylamino group or a fluorine atom. A good alkylcarbonylamino group, a substituted or unsubstituted phenylcarbonylamino group, an alkoxycarbonylamino group or a substituted or unsubstituted phenoxycarbonylamino group; Y represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom; ¹ and R ² each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an allyl group or a substituted or unsubstituted phenyl group), and an indoaniline-based thermal transfer recording dye represented by the formula: Thermal transfer recording sheet and thermal transfer ink using Make a summary.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The above general formula (I) used in the present invention
The nitrothiazole azo dye represented by is, for example, 2-amino-4-methyl-5-nitrothiazole represented by the following general formula (II)

[0010]

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(Wherein X, Y, R ¹ and R ² have the same meanings as in the above formula (I)) and can be obtained by a diazotization coupling reaction by a conventional method. . Specific examples of the nitrothiazole azo dye represented by the general formula (I) used in the present invention include those in which X, Y, R ¹ and R ² in the general formula (I) are as follows.

Examples of the alkyl group represented by X include a linear or branched alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group substituted by a fluorine atom include:
A trifluoromethyl group and the like; an alkoxy group includes a linear or branched alkoxy group having 1 to 8 carbon atoms; and a phenoxy group having a substituent includes a straight-chain or straight-chain alkoxy group having 1 to 8 carbon atoms. Chain or branched alkyl group, fluorine atom, chlorine atom, bromine atom, carbon number 1-4
Examples of the alkoxy group, nitro group, phenoxy group having a cyano group or a trifluoromethyl group as a substituent, and the like, a halogen atom, a fluorine atom, a chlorine atom, a bromine atom and the like, and an alkylcarbonylamino group Is an alkylcarbonylamino group having 2 to 9 carbon atoms such as an acetylamino group, a propionylamino group, and a butyroylamino group. Examples of the alkylcarbonylamino group substituted by a fluorine atom include a trifluoroacetylamino group. As the phenylcarbonylamino group having a substituent, the ring has 1 to 1 carbon atoms.
Phenylcarbonylamino having, as a substituent, a linear or branched alkyl group of 8, a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group having 1 to 4 carbon atoms, a nitro group, a cyano group, a trifluoromethyl group, etc. And the like. Examples of the alkoxycarbonylamino group include those having a linear or branched alkoxy group having 1 to 8 carbon atoms, and the substituted phenoxycarbonylamino group includes a carbon atom in the ring. A linear or branched alkyl group of Formulas 1 to 8, a fluorine atom, a chlorine atom,
Examples include a phenoxycarbonylamino group having a substituent such as a bromine atom, an alkoxy group having 1 to 4 carbon atoms, a nitro group, a cyano group, or a trifluoromethyl group. Particularly preferred examples of X include a hydrogen atom, a methyl group or an acetylamino group.

The alkyl group represented by Y includes a linear or branched alkyl group having 1 to 8 carbon atoms. The alkoxy group includes a linear or branched alkyl group having 1 to 8 carbon atoms. And a halogen atom is a fluorine atom, a chlorine atom or a bromine atom. Particularly advantageous values of Y include a hydrogen atom. As the alkyl group represented by R ¹ and R ² ,
Examples thereof include a linear or branched alkyl group having 1 to 8 carbon atoms, and examples of the substituted alkyl group include a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 4-hydroxybutyl group, and a 2-hydroxypropyl group. A carboxy-substituted alkyl group such as a hydroxy-substituted alkyl group, a carboxymethyl group, a 2-carboxyethyl group or a 3-carboxypropyl group; a cyano-substituted alkyl group such as a 2-cyanoethyl group or a cyanomethyl group; and an amino group such as a 2-aminoethyl group. Substituted alkyl group, 2-chloroethyl group, 3
-Chloropropyl group, 2-chloropropyl group or 2,
A halogen atom-substituted alkyl group such as a 2,2-trifluoroethyl group, a benzyl group, a p-chlorobenzyl group or 2
A phenyl-substituted alkyl group such as -phenylethyl group, 2
-(N) propoxyethyl group, 2- (iso) propoxyethyl group, 2- (n) butoxyethyl group, 2- (is
o) Alkoxy-substituted alkyl group such as butoxyethyl group, 2- (2-ethylhexyloxy) ethyl group, 3-methoxypropyl group, 4-methoxybutyl group or 2-methoxypropyl group, 2- (2-methoxyethoxy) ethyl Group, 2- (ethoxyethoxy) ethyl group, 2- (2-
(N) propoxyethoxy) ethyl group, 2- (2- (i
so) propoxyethoxy) ethyl group, 2- (2-
(N) butoxyethoxy) ethyl group, 2- (2- (is
o) butoxyethoxy) ethyl group or 2- {2- (2-
Alkoxyalkoxy-substituted alkyl groups such as ethylhexyloxy) ethoxydiethyl group, substituted alkyl groups such as 2-allyloxyethyl group, 2-phenoxyethyl group or 2-benzyloxyethyl group, 2-acetyloxyethyl group, 2-propionyl Oxyethyl group, 2-
(N) an acyloxy-substituted alkyl group such as a butyryloxyethyl group, a 2- (iso) butyryloxyethyl group or a 2-trifluoroacetyloxyethyl group, a methoxycarbonylmethyl group, an ethoxycarbonylmethyl group,
(N) propoxycarbonylmethyl group, (iso) propoxycarbonylmethyl group, (n) butoxycarbonylmethyl group, (iso) butoxycarbonylmethyl group, 2
-Ethylhexylcarbonylmethyl group, benzyloxycarbonylmethyl group, furfuryloxycarbonylmethyl group, tetrahydrofurfuryloxycarbonylmethyl group, 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2- (n) propoxycarbonylethyl group , (Iso) propoxycarbonylethyl group,
Substituted or unsubstituted (n) butoxycarbonylethyl, (iso) butoxycarbonylethyl, 2-ethylhexylcarbonylethyl, benzyloxycarbonylethyl, furfuryloxycarbonylethyl or tetrahydrofurfuryloxycarbonylethyl groups Alkoxycarbonyl-substituted alkyl group, 2-methoxycarbonyloxyethyl group, 2-ethoxycarbonyloxyethyl group, 2- (n) propoxycarbonyloxyethyl group, (iso) propoxycarbonyloxyethyl group, (n) butoxycarbonyloxyethyl group ,
(Iso) a substituted or unsubstituted alkoxycarbonyloxy such as a butoxycarbonyloxyethyl group, a 2-ethylhexylcarbonyloxyethyl group, a benzyloxycarbonyloxyethyl group, a furfuryloxycarbonyloxyethyl group or a tetrahydrofurfuryloxycarbonyloxyethyl group; Examples include a substituted alkyl group and a heterocyclic substituted alkyl group such as a furfuryl group or a tetrahydrofurfuryl group.

The substituted phenyl group represented by R ¹ and R ² includes, as a substituent, a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched chain having 1 to 4 carbon atoms. And those having a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, a nitro group, a cyano group and an alkyl group substituted by a fluorine atom such as a trifluoromethyl group.

Examples of the cycloalkyl group represented by R ¹ and R ² include a cyclopentyl group and a cyclohexyl group. Particularly preferred examples of R ¹ and R ² include a linear or branched alkyl group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, and an allyl group. More specific examples of the dye represented by the general formula (I) include those shown in Table 1.

[0016]

[Table 1]

[0017]

[Table 2]

[0018]

[Table 3]

[0019]

[Table 4]

[0020]

[Table 5]

[0021]

[Table 6]

[0022]

[Table 7]

[0023]

[Table 8]

When the dye of the present invention is used, an ink is prepared by dissolving or dispersing the dye in a medium together with a binder in a medium, the ink is coated on a base film, and dried to form a transfer sheet. create. As a binder for the preparation of ink, cellulose-based, acrylic, starch-based, epoxy-based water-soluble resin, acrylic resin, methacrylic resin, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyvinyl butyral, ethyl cellulose, Acetylcellulose,
Resins soluble in organic solvents such as polyester, AS resin and phenoxy resin can be mentioned.

As a medium for preparing the ink, in addition to water, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and isobutyl alcohol, cellosolves such as methyl cellosolve and ethyl cellosolve, toluene, xylene, chlorobenzene and the like can be used. Aromatics, acetates, esters such as butyl acetate,
Examples include ketones such as acetone, methyl ethyl ketone, and cyclohexanone; chlorinated solvents such as methylene chloride, chloroform, and trichloroethylene; ethers such as tetrahydrofuran and dioxane; and organic solvents such as N, N-dimethylformamide and N-methylpyrrolidone. .

In the above-mentioned ink, in addition to the above components, if necessary, organic and inorganic non-sublimable fine particles, a dispersant, an antistatic agent, an antifoaming agent, an antioxidant, a viscosity modifier and the like are used. Can be added. As a base film for applying ink for preparing a transfer sheet, thin paper such as condenser paper and glassine paper, and a heat-resistant plastic film such as polyester, polycarbonate, polyamide, polyimide and polyaramid are suitable. ,
Their thickness can range from 3 to 50 μm.

Of the above base films, a polyethylene terephthalate film is particularly advantageous in consideration of mechanical strength, solvent resistance, economy and the like. However, in some cases, the polyethylene terephthalate film does not always have sufficient heat resistance and the running performance of the thermal head is insufficient, so that a heat-resistant resin containing a lubricant, heat-resistant fine particles, etc. on the opposite surface of the coloring material layer By providing a layer of
A thermal head having improved running properties can be used.

As a method of applying the ink to the base film, a gravure coater, a reverse roll coater,
The coating can be carried out using a rod coater, an air doctor coater, or the like.
What is necessary is just to apply so that it may be in the range of 1-5 micrometers. The heat-sensitive transfer sheet of the present invention can use not only a thermal head but also an infrared ray or a laser beam as a heating means. In addition, a current-carrying film that generates heat by passing electricity through the base film itself can be used as a current-carrying dye transfer sheet. The thermal transfer ink of the present invention can also be used in a method of heating and evaporating with a heater and directly recording on recording paper without applying the ink to a sheet. At this time, an ink containing no binder is advantageous as the ink.

[0029]

The present invention will be described in detail with reference to the following examples. Example 1 Table 1, No. The following transfer recording test was performed using one dye. a) Preparation of ink 6 parts by weight of the above pigment 10 parts by weight of AS resin (Product name: Denka AS-S; product of Denki Kagaku Kogyo Co., Ltd.) 24 parts by weight of methyl ethyl ketone 60 parts by weight of toluene Total 100 parts by weight A mixture of the above composition is painted. The mixture was treated with a conditioner for 30 minutes to prepare an ink.

B) Preparation of transfer sheet A polyethylene terephthalate film (6 μm
Thick) and dried (dry film thickness: about 2 μm) to obtain a transfer sheet. The heat-resistant lubrication treatment of the polyethylene terephthalate film is performed by adding 10 parts by weight of an acrylic resin (trade name: BR-80; a product of Mitsubishi Rayon Co., Ltd.) to the polyethylene terephthalate film, amino-modified silicone oil (trade name: KF393; Company product) 1
The coating was performed by applying a liquid composed of 89 parts by weight of toluene and 89 parts by weight of toluene and drying (dry film thickness: about 1 μm).

C) Preparation of Image Receptor 70 parts by weight of polyvinyl phenyl acetal resin, 30 parts by weight of vinyl chloride / vinyl acetate / vinyl acetal copolymer resin (trade name: Esrec A; product of Sekisui Chemical Co., Ltd.), silicone varnish (product) Name: TSR-160, solid content concentration 60%; Toshiba Silicone Co., Ltd. product) 30 parts by weight, hexamethylene diisocyanate compound (trade name: Mytec NY-710A, solid content concentration 75%; Mitsubishi Chemical Co., Ltd. product) 15 weight parts Parts, amino-modified silicone oil (trade name: KF393; product of Shin-Etsu Chemical Co., Ltd.) 2.5 parts by weight, methyl ethyl ketone 600 parts by weight,
A liquid consisting of 600 parts by weight of toluene is applied to a synthetic paper (product name: YUPO FPG150; product of Oji Yuka Co., Ltd.) using a wire bar, dried (dry film thickness: about 5 μm), and further treated in an oven at 80 ° C. for 2 hours. In this way, it was produced.

D) Transfer Recording The ink-coated surface of the transfer sheet is superimposed on the resin-coated surface of the image receiving body, and is fed in the feed direction using a partial Grace type line thermal head having a heating resistor density of 5.6 dots / mm. Then, recording was performed at 6 lines (dots) / mm, at a speed of 16 ms / line, at an applied power of 0.20 W / dot, and with an energizing time per line of 14 ms.

E) Measurement of Color Density A blue recording was obtained by the method d), and the color density of the recording was measured using a reflection densitometer (trade name: Macbeth RD-927;
Macbeth product) using an orthomatic filter. Table 2 shows the measurement results of the color density. In addition,
The dye used in this example was 2-amino-4-methyl-5.
-Nitrothiazole is diazotized with nitrosylsulfuric acid by a conventional method, and coupled to N, N- (n) dibutylaniline to synthesize. λmax (in acetonitrile): 590 nm.

Examples 2 to 10 In place of the dyes used in Example 1, Table 1, 2-N
o. 10 and No. Preparation of ink, preparation of transfer sheet, transfer recording,
The color density was measured. Table 2 shows the measurement results of the color density. Comparative Examples 1-10 Preparation of ink, preparation of transfer sheet, transfer recording, measurement of color density in the same manner as in Example 1 except that dyes A to J described below were used instead of the dyes used in Example 1. Did. Table 2 shows the measurement results of the color density.

[0035]

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[0036]

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Example 12 In the same manner as in Example 1 except that the dye used in Example 1 was replaced with a mixture of the following dyes, an ink was prepared (total amount of the ink mixture was 102 parts by weight), and a transfer sheet was prepared. As a result of the transfer recording, a black recorded matter was obtained. As a result of measuring the color density of the recorded matter in the same manner as in Example 1, 1.9 was obtained.
It was 5.

[0038]

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Comparative Example 11 In place of the dye (a) used in Example 11,
Preparation of an ink, preparation of a transfer sheet, and transfer recording were performed in the same manner as in Example 11 except that the dye 5-1 described in Example 1 of JP-A-276670 was used. As a result, a black recorded matter was obtained. The color density of the recorded matter was measured in the same manner as in Example 11, and the result was 1.75.

[0040]

[Table 9]

[0041]

The thermal transfer recording using the nitrothiazole azo dye of the present invention makes it possible to obtain a recorded matter having a high color density with respect to an orthomatic filter. Thus, a black recorded matter having a high color density can be obtained.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takashi Morishima 1000 Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa Pref.

Claims (3)

[Claims] 1. A compound represented by the following general formula (I) (Wherein X is a hydrogen atom, an alkyl group optionally substituted by a fluorine atom, an alkoxy group, a substituted or unsubstituted phenoxy group, a halogen atom, a formylamino group,
Represents an alkylcarbonylamino group which may be substituted by a fluorine atom, a substituted or unsubstituted phenylcarbonylamino group, an alkoxycarbonylamino group or a substituted or unsubstituted phenoxycarbonylamino group;
Y represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, and R ¹ and R ² each independently represent a hydrogen atom,
Substituted or unsubstituted alkyl group, cycloalkyl group,
Represents an allyl group or a substituted or unsubstituted phenyl group)
A nitrothiazole azo dye for thermal transfer recording represented by the formula: 2. A thermal transfer recording sheet having a coloring material layer containing a nitrothiazole azo dye of the general formula (I) and a binder on a substrate. 3. A thermal transfer ink containing the nitrothiazole azo dye of the general formula (I) and an organic solvent.